Rubber composition and method of making same



Patented July 29, 1947 Stewart L. Bram, Dayton, Ohio, asslgnor to General Motors Corporation, Detroit, Mich, a corporation of Delaware s No Drawing. Application February 23, 1944,

Serial No. 523,574 Q 7Claims. (cl. 260-41).

This invention relates to an adhesive composition for cementing rubber or rubberlike material to metal and to a method for manufacturins such a composition, this application being a in the metal part is brass plated and wherein a perfect coating of brass over the metal is necessary to obtain a consistently good bond. This typeof bond has. proved satisfactory but is expensive and requires critical control in order that perfect brass plate is obtained. Other cement types of bonds are utilized wherein the thermoplasticity or the bond is not satisfactory or wherein toxic solvents and thinners or expensive solinvention is directed to a cement which eliminates continuation in part of my copending appiica- 5 the prior difliculties in that it is inexpensive,- utii n rial No. 4 4,17 filed Jan ry 1943- .lizes petroleum naphtha solvents in most formula- An object of the invention i o pmvide 'tions and will provide a strong bond when used 1 hesive compound which will form a iv bonds with or without brass plating and will provide between rubberor rubber-like material and metal extremely good bonds t brass m t whereparts h as el. ir n, brass and aluminum, e 1 in the continuity of the plating is not sufliciently In yi o t t above o i t it i a satisfactory to provide a good bond with the ther .object to provide a cement which includes prior art t In other words, t use of large quantities of channel carbon black having the brass plating W111 immovethe strength of a surface area Within P' range the bond but the cement may be used without which carbon black is incorporated in the rub- 16 the brass plate if desired, in any case no her or rubbernke material and wherein the critical control is required in the plating since we mixture Carrie? by a suit-able solvent the continuous plate is not'necessary to success. A still further oblect of the invention is 'to The invention is primarily concerned with a provide an adhesive compound wherein rubber cement composition composed ofrubber or synor rubberlike material is utilized together with 80 theme rubber and channel carbon black v channel carbqn black having gram size prefer in channel carbon black is incorporated in the ably of 28 millimicrons and wherein the chanrubber in quantities greater than 100% of the carbon black is in quantities greater than rubber together with a suitable solvent to make 100% of the rubber. In some instances it may the cement fluid Channel carbon black is a v be desirable to include plasticizers, accelerators, 26 hard type of carbbn black which produces age'resistors or vulcanizmg agents together with sion resistance in rubber and is highly reenforcresinous materials an example of K 3 ing thereto. The mixture of rubber or syncyclized rubber known in the trade as Pliolite. thetic rubber and oh nn 81 carbon black is i'TheSe addition agents may Vary according to the thinned to a suitable v iscosit with a suitable use of the compound andto the rubber .ingredirubber or s nthetic rubb solfient Such as ent g for example natural rubber or syntroleum naghtha or suit ble aromatic solve is thetic ru ber:

In carrying out all of the above objects it'is gagg g i g g Fi g i f g g still another object of the invention to provide g m i y 1-, f th na l; n a method for incorporating large quantitie of so as O a ig fi n channel black into rubber or rubberlike material. 5 metal er w 9 part presse Further objects and advantages of the, present together w th unclfred rubber compound invention will be apparent from the f ll ing 7} der suitable pressure in a mold and cured at a description a suitable temperature to produce an adhesion There has been a need for suitable cement 40 bond having Ptimum characteristlcsz In m compositions for providing an adhesion bond beinstances it may be desirable to use mtermedl' tween rubber or rubberlike material and metal cements of conventional yp rubber parts. Heretofore numerous'attempts have been pounds or tie gums. In some instances two made to fomulat such cement but 1 t coats of the cement may be desirable. In determost part the results are limited to bonds where.- mining these factors it is best to use the trial method to obtain a bond of the desired strength.

Bonds between rubber and unplated metal having a tensile strength in excess of 800 pounds ,per square inch have been obtained wherein the rubber stock is a 3200 pound per square inch type.

merized chloroprene series, having a specific gravity of 1.37, a. hardness of 59, with an 1800 pounds per square inch tensile strength and 575% elongation at break was cemented to 1020 steel, grit blasted and electrocleaned and the adhesion was noted to be in the neighborhood of 550 lbs. per square inch. Using the same materials but with brass plate steel an increase of adhesion was noted and in this instance a 965 pounds per square inch adhesion was obtained.

Using a Buna S synthetic rubber stock of 1.18 specific gravity, 70 hardness, 2900 pounds per sq. inch tensile strength and 450% elongation at break it was possible to get an adhesion of 900 pounds per square inch on grit blasted brass plated 1020 S. A. E. steel. In all instances the tensile tests were carried out under the standard A. S. T. M. procedure. Another interesting fact is that natural rubber may be bonded to metal through the use of a synthetic rubber cement. For example, Buna S cement to be described in more detail hereinafter, gives an adhesion in excess of 1000 pounds per square inch in conjunction with natural rubber stock and brass plated steel wherein the rubber had a tensile strength of 4,000 pounds per square inch, an elongation of 575% at break and a hardness 64. All hardness figures noted herein are Shore durometer A readings.

A One factor which is extremely important in connection with my invention has to do with the surface area of channel carbon black. Channel carbon blacks are colloidal carbons which'have a wide range of particle sizes. I have found that' the blacks which are suitable in connection with my invention are those having particle sizes ranging between 3 millimicrons and 100 millimicrons as measured by an electron microscope using the method disclosed in Rubber Chemistry and Technology, vol. 15, page 657 (1942), said. article being written by W. P. Wiegand. I have found that the optimum results can-be obtained by using a 28 millimicron carbon black in quantities of over 100% by weight of the rubber or rubber like material. However, I have also found that the millimicron size of carbon black may be reduced providing the total quantity of channel carbon black does not have a surface area substantially greater than the surface areaof the preferred quantity of carbon black having "a 28 millimicron size. In

other words, in utilizing a formula having 100 parts rubber therein I have found that .the channel carbon black of a 28 millimicron size may vary between 101 parts to 300 parts with good results. Thus, if a 21 millimicron carbon black is used it shouldbespeciflcally noted that the surface area of the carbon black used should not exceed. a surface area of a 28 millimicron carbon black withinthe range noted; since the surface area of the 21 millimicron carbon black is substantially greater it is obvious that the total weight must be cut down. Similarly, larger carbon blacks may be utilized, but here again the same factors must be taken into consideration.

by 28 millimicron carbon black in the range above mentioned.

Specifically various formulas of compounds may be made allof which will be satisfactory under one or more conditions of use, but as previousiv noted in each case it is desirable to make up the compound and test it for this specific use in order'to determine which compound will yield the most satisfactory results. In connection with natural rubber the following formula giving a range of ingredients has yielded very satisfactory results and it should be noted in this formula and in succeeding formula where no mention of the particle size of channel carbon blacli is noted that the carbon black should be a'28 millimicron mixtures of different blacks of other millimicron sizes having equivalent surface areas.

Parts Suitable solvent as required In the above formula where an activator, such as zinc oxide, is used toward the upper end of the range, the quantity of channel carbon black may be reduced in some instances since both ingredients act as a reenfoncing agent to some eatent. In all cases the quantities of rubber and channel carbon black must be'in excess of the quantity of the other ingredients and the composition must be compounded'so as to produce a rubber to metal adhesion cement after curing under pressure. While the above formula gives a wide variation in the quantities of ingredients to be used, it will be noted that'the main ingredients are rubber and channel carbon black together with the solvent and these are .the important ingredients and form the basis of the such'material preferably being cyclized rubber which is sold under the trade name of Pliolite which is a product of rubber with tin-tetra-chloride or chlorostannic acid added wherein the rubcarbon black or quantities of carbon black or her is cyclized with the tin compound with the addition of heat and a solvent. The grade preferred is a horny, tough material which is relatively brittle at room temperature. Other materials such .as hardened wood resin may be substituted for this cyclized rubber with satisfactory results as well as other rubber derivatives which In some instances it is highly desirable to use a mixture, for example, when using in the neighborhood of parts of rubber a satisfactory cement has been made up using 104 parts of 25 millimicron carbon black and 26 parts of 3 millimicron carbon black. In this instance the total surface area is within the limits noted, namely.

within the limits of the surface area determined act as stiffening fillers. The preferred formulas which have been utilized with great successare as follows:

' Parts Chemically plasticizedvrubber 20.5 Cyclized rubber .l6.6 Dibutyl phthalate 8.6 Zinc oxide (Fr. process) 1.0

Sym. di beta naphthyl-para-phenylenediamine 7 Channel carbon black (28 millimicron) 51.5 Sulphur V 1.0

Suitable solvent to secure desired viscosity.

I Suitable solvent to secure desired viscosity.

When using a synthetic rubber such as neoprene the following formula-with ranges of ingredients is given:

' Parts Neoprene (CG type) r. 100 Plasticizer (di-butyl-phthalate) 0450 French process zinc oxide -20- Light calcined magnesians 0-20 Channel carbon black (28 millimicron) 101-300 Suitable solvent as required The ingredient in this formula may vary for its specific use and in connection with the specific materials to be bonded. A preferred formula for a neoprene cement is as follows:

Parts Neoprene (CG type) 175 Di-butyl phthalate 63 French process zinc oxide 10 Light calcined magnesia", 10 Channel carbon black (28 millimicron) 450. Suitable solvent as required When using a Buna S type synthetic rubber the following formula with ranges ofingredients may be used:

, 7 Parts Buna S rubber 50 French process zinc oxide 020 Plasticizer (di-butyl phthalate) .0-100 Ager (symmetrical di-beta-naphthylpara-phenylenediamine) 0-20- Sulphur 0-40 Channel carbon black (28 millimicron) l -150 Suitable solvent as required Two specific formulas of the Buna S type adhesive which have yielded exceptionally good results are as follows:

Formula 1 Parts Buna S rubber 200 French process zinc oxide Di-butyl-phthalate 130 Symmetrical di-beta-naphthyl-para-phenylenediamine 10 Sulphur 20, Channel carbon black (25 millimicron size) 425 Suitable solvent as required Formula 2 Buna S rubber 92 Zinc oxide 3 Di-butyl-phthalate 32 Symmetrical di-beta-naphthyl-para-phenylenediamine 3 Sulphur 8 Channel carbon black (25 millimicron size) 104 Channel carbon black (3 millimicron)---" 26 Mercapto-benzo-thiazole (accelerator) Suitable solvent as required.

In the foregoing Buna S formula it has been found that Buna N type rubber may be substituted together with a 28 millimicron. carbon black and a solvent of the benzol-toluene family. However, the Buna N type cements are of chalky consistency when dried and, therefore, do not provide as satisfactory a bond as do the Buna S type cements. However, Buna N cements have pulled up to 800 pounds per square inch on brass plate on adhesion tests and under some conditions may be used.

The method of manufacturing the compositions set forth herein is of particular importance and so far as I am aware the method to be described hereinafter is the only method by which large quantities of channel carbon black as noted, can

be incorporated with rubber, or synthetic rubbers.

I found it impossible to combine these two mafterials satisfactorily in the quantities noted on an ordinary rubber mill and have found it necessary to provide an entirely new method. The only satisfactory way to my knowledge of making this composition is to take the dry ingredients namely, rubber and channel carbon black with or without the other materials and place them in an internal type mixer of the Werner Pfieiderer type and close the mixer except for a vent and solvent inlet. The mixer is preferably cooled by running a cooling fluid through the jacket thereof. The mixer is then started and solvent is fed in small increments at short intervals ,of time until the mix approximates a. heavy paste or dough, whereuponthe addition of solvent can be increased until a smooth homogeneous cement results. It is important that the rate of addition of the solvent and the quantities of the additions are carefully controlled, otherwise the cement will not be of ,the best quality attainable.by this method. A

etc., are added in the dry state to a .7 gallon.

Werner Pfleiderer mixer equipped with kneading blades, and in this instance a total non-volatile 'weight of 750 grams is utilized. The mixer is i started and 2 cc. of petroleum naphtha solvent are added each minute until the-desired dilution is reached. As the dough forms and thins the dilution may be accelerated, that is the rate of 2 cc. per minute may be increased to speed the dilution. In this instance a 2 cc. addition of solvent may occur each minute or 2 cc. of solvent.

never a sufficient quantity present to cause the mixture to be lumpy. Diflerent solvent feed schedules may be used. but the optimum cycle should be determined for each formula by trial. In the foregoing, it will be apparent that I have provided a new cement and method for making the same which provides strong adhesion bonds between rubber or synthetic rubber and metal parts when applied thereto and which cement is relatively inexpensive to manufacture and when manufactured by the method disclosed herein is relatively easy to compound.

In the appended claims the words rubberlike material" or rubber ingredient" etc., include that class of compounds comprising natural rubbers,

neoprene, Buna S type synthetic rubber or Buna N type synthetic rubber, orany synthetic polymer or co-polymer corresponding to rubber.

While the embodiments of the present invention as herein disclosed, constitute preferred forms, it is to be-"understood that other forms a 7 might be adopted, all coming within the scope of .e the claims which follow.

What is claimed is as follows:

1. A liquid rubber composition adapted to be used as a cement between rubberlike materials and metal parts comprising: natural rubber-20 parts; cyclized rubber-16 parts; a plasticizer-8 parts; zinc .oxide-l part; black-51parts, said channel carbon black being of a 28 millimicron size or its surface area equivalent wherein the particle size of the channel carbon black may vary between 3 to 100 millimicrons; sulphur one part together with a solvent for the natural rubber and cyclized rubber.

2. A liquid rubber composition adapted to be used as a cement between rubberlike material and metal parts comprising: natural rubber 20.5 parts, cyclized rubber 16.6 parts, channel carbon black, 51.5 parts, said channel carbon black being of a 28 miliimicron size or its surface area equivalent wherein the particle size may vary between-3 and 100 millimicrons mixed with a plasticizer. activator, age resistor and vulcanizer, said ingredients being in a fluid condition through the action or a solvent for the rubber and cyclized rubber.

,3. A liquid rubberlike composition adapted to be used as a cement between rubberlike materials and metal parts comprising: a rubbery ingredient, selected from the class, consisting of natural rubber, polychloroprene and butadiene channel carbon styrene co-polymer 100 parts, and having incorporated therein channel carbon black in excess of the rubbery ingredient, wherein the channel carbon black has a particle size within the range of 3 to 100 millimicrons, the quantity of said channel carbon black having a surface area equal to the surface area of from 101 to 300 parts of a 28 millimicron particle size channel carbon black, and a solvent for the rubbery ingredient.

4. A liquid rubberlike composition adapted to be used as a cement between rubberlike materials and metal parts comprising: an elastomer, consisting of, a butadiene-styrene co-polymer 100 parts, and having incorporated therein channel carbon black in excess of the co-polymer wherein the channel carbon black has a particle size within a range of from 3 to 100 millimicrons, the quantity of said channel carbon black having a surface area equal to the surface area of from 101 to 300'parts of a 28 millimicron particle size channel blaclr, and a solvent for the copolymer.

5. In a method of making rubberlike cement including a rubberlike material, consisting of; butadiene styrene co-polymer together with channel carbon black having a particle size of from- 3 to 100 millimicron in quantities in=excess oi the co polymer wherein the quantity of channel black has a surface area equal to the surface area of 101 to 300 parts of a 28 millimicron particle size channel carbon black, the steps comprising: supplying all of the co-polymer and channel carbon black'in the dry state to an internal type mixer, mixing the two ingredients and simultaneously adding measured small quantities of a solvent for the co-polymer until the mixture becomesa smooth dough-like consistency, and then increasing the addition of solvent and continuing the mixing until the consistency of the mixture is that desired.

6. A liquid rubberlike composition adapted to be used as a cement between rubberlike materials and metal parts, comprising in combination; rubber 100 parts-andchannel carbon black in excess of the rubber, wherein the channel carbon black has a particle size within a range of 3 to 100 millimicrons, the quantity of said channel carbon black being equal in surface area to from 101 to 300 parts of a 28 miliimicron siz channel carbon black, and a solvent for the rubber.

7.. A liquid rubberlike composition adapted-to be used as a cement between rubberlike materials and metal parts, comprising in combination; polychloroprene, 100 parts and channel carbon black in exces's'of the polychloroprene wherein the channel carbon black has a particle size within a range of 3 to millimicrons, the quantity of said channel carbon black being equal in surface area. to from 101 to 300 parts of a 28 milliniicron size channel carbon black, and a solvent for the polychloroprene \S'I'EWART L. BEAMS.

REFERENCES CITED The following references are of record in the 2,233,985 Knowland et al. Mar. 4, 1941 

